S(alkllthio ethyl) phosphorothioamidate

ABSTRACT

A phosphorothioamidate having the formula, WHEREIN R1 is an alkyl having up to four carbon atoms, R2 and R3 are individually a hydrogen atom, an alkyl having up to 10 carbon atoms, a cycloalkyl having up to 6 carbon atoms, a phenyl, an aralkyl having up to eight carbon atoms or an alkenyl having up to five carbon atoms, R4 and R5 are each alkyl having up to five carbon atoms, and X is an oxygen or sulfur atom, which may be effectively used as an insecticidal, acaricidal and fungicidal composition. The phosphorothioamidate is prepared by (1) dealkylating a thionophosphoric acid amidate having the formula, WHEREIN R1, R2 and R3 are as defined above, with an alkali hydrosulfide, to prepare a phosphate having the formula, (2) CONDENSING THE THUS OBTAINED PHOSPHATE WITH A HALOGEN COMPOUND HAVING THE FORMULA, WHEREIN Hal represents a halogen atom, and R4, R5 and X are as defined above.

United States Patent Tsuchiya et al.

[4 June 13, 1972 [54] S(ALKLLTHIO ETHYL) PHOSPHOROTHIOAMIDATE 22 Filed: Nov. 10, I969 211 Appl. No.: 875,565

[52] US. Cl. ..260/948, 260/609 R, 260/959,

260/979, 260/987, 424/216 ..C07f 9/24, AOln 9/36 ..260/948 [5]] lnt.Cl [58] Field of Search [56] References Cited UNITED STATES PATENTS 2,959,516 l l/l960 Sallmann ..260/948 X Primary Examiner-Joseph Rebold Assistant Examiner-Anton H. Sutto Attorney-Stevens, Davis, Miller & Mosher [5 7] ABSTRACT A phosphorothioamidate having the formula,

N'i -S-CH- CHzS Rt s (I) R1 IIQX R,

wherein R, is an alkyl having up to four carbon atoms, R, and R, are individually a hydrogen atom, an alkyl having up to 10 carbon atoms, a cycloalkyl having up to 6 carbon atoms, a phenyl, an aralkyl having up to eight carbon atoms or an alkenyl having up to five carbon atoms, R, and R, are each alkyl having up to five carbon atoms, and X is an oxygen or sulfur atom, which may be effectively used as an insecticidal, acaricidal and fungicidal composition.

The phosphorothioamidate is prepared by (l) dealkylating a thionophosphoric acid amidate having the formula,

/Rr (mmd -N wherein R,, R, and R are as defined above, with an alkali hydrosulfide, to prepare a phosphate having the formula,

(2) condensing the thus obtained phosphate with a halogen compound having the formula,

HaLCH-CHzSR;

C HzX R wherein Hal represents a halogen atom, and R R, and X are as defined above.

9 Claims, No Drawings S(ALKLLTH1O ETHYL) PHOSPHOROTHIOAMIDATE This invention relates to phosphorothioamidate, a process for preparing the same and a novel systemic insecticidal, acaricidal and fungicidal composition, characterized by containing the same as an active ingredient, which is eflective for the control of injurious insects and plant diseases.

More particularly, the invention pertains to l a novel phosphorothioamidate represented by the formula,

wherein R,, R and R are as defined above, with an alkali hydrosulfide represented by the formula,

MSH (Il wherein M is an alkali metal atom, to obtain a phosphate represented by the formula,

wherein R,, R,, R, and M are as defined above, and then condensing said phosphate with a halogen compound represented by the formula,

CIIgXRa wherein Hal represents a halogen atom, and R.., R, and X are as defined above.

In the process of the present invention, thionoamidate represented by the formula,

when the wherein R is as defined above, is used, the dealkylating reaction may be conducted by using an alkali hydroxide represented by the formula,

MOH

wherein M is as defined above.

The thionoamidate represented byahe formula (ll) may be obtained by the method described in Z. obr. chim. 25 828.

The present compounds represented by the formula (1) are particularly suitable for the control of injurious insects, and can most effectively exterminate planthoppers, mites, stem borers, scales and nematodes as well as injurious insect belonging to Arthropoda such as Lepidoptera, Diptera, Coleop tera and Hemiptera. What is to be worthy ofspecial mention is that the present compounds are excellent not only in contact and stomach insecticidal action but also in systemic insecticidal action and have prominent acaricidal actions on mites rice Helminthosporium leaf spot, rice sheath blight and the.

like. The present compounds have excellent characteristics, which have never been seen heretofore. in that they can show insecticidal and acaricidal actions simultaneously with fungicidal actions. Thus, the present compounds are markedly useful as agricultural insecticides, acaricides and fungicides.

The present invention also relates to (3) a novel, systemic insecticidal, acaricidal and fungicidal composition, characterized by containing as an active ingredient at least one phosphorothioamidate represented by the formula (I).

The present compounds are synthesized in the following manner:

An alkali hydroxide, eg sodium hydroxide or potassium hydroxide, is dissolved in a suitable solvent, e.g. an alcohol such as methanol, ethanol or methyl cellosolve, water, N,N- dimethylformamide or dimethyl sulfoxide, and the solution is saturated with hydrogen sulfide to obtain a solution of an alkali hydrosulfide represented by the formula (lll). To this solution is added the thionoamidate represented by the formula (II), and the mixture is heated with stirring to dealkylate said thionoamidate, whereby a crystalline or viscous liquid phosphate represented by the formula (IV) is obtained. The thus obtained phosphate is isolated and is dissolved in a suitable solvent, e.g. an alcohol such as methyl alcohol or ethyl alcohol, a ketone such as methylethylketone or acetone, or water, and is then condensed with a halogen compound represented by the formula (V), whereby a desired phosphorothioamidate represented by the formula (I) can be easily obtained in a high yield. In some cases, the phosphate may be condensed without being isolated or without being dissolved in a solvent.

The temperature employed in the dealkylation reaction varies depending on the kind of starting materials and solvent employed, but may be the reflux temperature of the solvent, in general. The reaction time is from several hours to several times ten hours. Further, the reaction temperature and time employed in the condensation reaction with halogen compound (V) are 50-80 C. and 30 minutes to 3 hours. in the above manner, a desired compound can be obtained in a satisfactory yield.

A number of examples of the starting materials employed in practicing the present invention, i.e, thionoamidates (ll), alkali hydrosulfides (Ill), and halogen compounds (V), are shown below, but it is needless to say that these are not limitatlve.

Thionoamidates:

0,0-Dimethyl-phosphorothionoamidate 0,0-Diethyl-phosphorothionoamidate 0,0-Di-n-propyl-phosphorothionoamidate 0,0Di-iso-propyl-phosphorothionoamidate 0,0-Di-n-butyl-phosphorothionoamidate 0,0-Diethy]-N-phenyl phosphorothionoamidare QODiethyl-N-benzyl-phosphorothionoamidate 0,0-Diethyl-N-cyclohexyl-phosphorothionoamidate 0,0-Diethyl-N-n-butyl-phosphorothionoamidate 0,0-Diethyl-N-n-propyl-phosphorothionoamidate 0,0-diethyl-N-ethyl-phosphorothionoamidate 0,0-diethyl-N-methyl-phosphorothionoamidate 0,0-Diethyl-N,N-diethyl-phosphorothionoamidate 0,0-Dimethyl N-n propyl-phosphorothionoamidate 0,0-Dimethyl-N-n-butyl-phosphorothionoamidate 0,0-Dimethyl'N-phenyl-phosphorothionoamidate 0,0Dimethyl-N,N-diethyl-phosphorothionoamidate 0,0-DimethyLN-iso-propyl-phosphorothionoamidate 0,0-Dimethyl-N,N-dimethyl-phosphorothionoamidate 0,0-Dimethyl-N-allyl-phosphorothionoamidate 0,0-Dimethyl-N,N'diallyl-phosphorothionoamidate 0,0-dimethyl-N-allyl-phosphorothionoamidate 0,0-Diethyl-N,N-diallylphosphorothionoamidate Hydrosulfides:

Sodium hydrosulfide Potassium hydrosulfide Halogen compounds:

accordance with the present invention are shown below.

1 ,S-Diethyllhio-Z-chloropropane l ,3-Di-n-propylthio-Z-chloropropane l ethylthio-3 ethoxy-2-chloropropane l -ethylthio-3-methoxy-2-chloropropane l -iso-Propylthio- 3-n-propoxy-2-chloropropane A number of examples of typical phosphorothioamidates in Compound No. Structural formula CzHs CHzO CH;

O CH: CHzUCH:

In practical application, the present compounds may be used singly without the addition of other ingredients or, for easier application of the compounds as controlling chemicals, they may be used in admixture with carriers. Ordinarily, the present compounds are formulated into any optional forms such as emulsifiable concentrates, wettable powders, oil sprays, dusts, irrigants, seed-coating powders, granules, aerosols, fumigants, etc., according to processes thoroughly known to those skilled in the art without necessitating any special conditions, like in the case of common organophosphorus chemicals, and can be made into any desired forms by use of carriers and may be used for any desired purposes. Further, they may be used in admixture with one or more of other chemicals to make the effects thereof broader and higher. For example, they can be used in admixture with organo-phosphorus type insecticides such as 0,0-dimethyl O- (3-methyl-4-nitrophenyl)phosphorothioate, 0,0-dimethyl S- (N-methylcarbamoyl )methyl phosphorodithioate, etc.; pyrethroid type insecticides such as Allethrin, phthalthrin, etc.; organochlorine type insecticides such as BHC, DDT, etc.; carbamate type insecticides such as 3,4-dimethylphenyl-N- methylcarbamate, l-naphthyl-Nmethylcarbamate, etc.; organo-sulfur type fungicides such as pentachlorobenzyl alcohol, pentachlorobenzaldoxime, etc.', and organo-arsenic type fungicides. Further, they are easily miscible with herbicides, fertilizers plant growth-controlling agents, synergists, attractants, repellents and the like chemicals to give multiurpose compositions and, depending on combinations, synergistic effects can be expected.

in order to clarify the excellent characteristics and effects of the present compounds, typical test results are shown below with reference to test examples. In the test examples, the numerals in the parentheses represent the numbers of the present compounds exemplified before.

Test Example I A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of adults of two-spotted red spider mites (Terranichus telarius). The leaves of the kidney bean plant parasitized with said mites were immersed for l minute in an aqueous dilute solution of each of the present compounds in the form of wettable powders, and water was fed so as not to wither the leaves. After 48 hours, the alive and dead of the spider mites were observed by means of a magnifying glass and, from the mortality, LCSO values were calculated according to Finney's simplified iconography to obtain the results set forth in Table TABLE 1 Compound No. LC50 (times) 200,000 Dimethoate 500,00 Akal' 100.000

' Registered trade name for an insecticide produced by Geigy Co.

Test Example 2 Insecticidal effects on smaller brown planthoppers: air-drymg,

A rice seedling (height lS-20 cm), which had elapsed days after germination, was immersed for 1 minute in an aqueous dilute emulsion at a given concentration of each of the present compounds in the form of emulsifiable concentrates. Afier air-during the rice seedling was put in a large test tube. into the test tube were liberated -30 smaller brown planthoppers, and the tube was covered with gauze. After 24 hours, the alive and dead of the planthoppers were observed and, from the mortality, LCSO values were calculated according to Finneys iconograph to obtain the results as set forth in Table 2.

TABLE 2 Compound No. LCSO (times) Test Example 3 A potted mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of spider mites, and was dusted by use of a bell jar duster with 4 Kg/lO ares of each of the present compounds in the form of 3 percent. dusts. Alter the dusting, the plant was further parasitized on difl'erent days with two-spotted red spider mite adults, and the mortalities of the insects alter 48 hours were individually investigated to obtain the results as set forth in Table 3.

Test Example 4 A mottled kidney bean plant was grown to the 2 leaves stage in a flower pot of 9 cm. in diameter. The root portion of the plant was sprinkled with 6 Kg/IO ares of each of the present compounds in the form of 3 percent granules. At the same time, the leaves of the plant were parasitized with a large number of two-spotted red spider mite adults. After 72 hours, the leaves were cut and taken up, and the alive and dead of the mites were observed by means of a magnifying glass to obtain the results as set forth in Table 4 Test Example 5 A rice plant at the offshoot stage, which had elapsed 30 days after planting, was transplanted in a pot, and eggs of rice stem borers immediately before hatching were laid on the stem of the plant. After 4 days, the plant was sprinkled with each of the present compounds in the form of Speroent granules. 5 Days thereafier, the plant was taken up from the pot, and the stern was broken to observe the alive and dead of the larvae in the stem. The results were as set forth in Table 5.

Test Example 6 A young mandarin orange tree of 3 years old was parasitized with a large number of arrowhead scales (Unapsis Yanonensir). To the trunk of said tree (at a portion of 10 cm above the ground) was applied in the fonn of a ring 5 cc/ l cm of an emulsion formed by diluting to l,000 times each of the present compounds in the form of 50 percent emulsifiable concentrates. On the day before, and 3, 7, l0 and 20 days alter of ap plication of the chemical, the habitat densities of the insects were investigated to obtain the results as set forth in Table 6.

TABLE 6 Change in habitat density before and after application of chemical.

Days before application Days alter application of chemical The numerals show the average numbers of insects per 30 leaves. Test Example 7 A rice plant at the optimum offshoot stage, which had elapsed 35 days after planting, was transplanted in a flower pot, and eggs of rice stern borers immediately before hatching were laid on the stern of the plant. After days, the rice plant was sprayed with 6 ml/pot of an aqueous dilute emulsion of each of the present compounds in the form of emulsifiable concentrates. 4 Days thereafter, the stern was broken to ob serve the alive and dead of the larvae of rice stem borersv The results were as set forth in Table 7.

nitrophenyl phosphorothioate l .000 98.4

Test Example 8 A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days alter sowing, was parasitized with a large number of adults of two-spotted red spider mites (Tetmnychm telariur). The leaves of the kidney bean plant parasitized with said mites were immersed for 1 minute in an aqueous dilute solution of each of the present compounds in the form of wettable powders, and water was fed so m not to wither the leaves. Afier 48 hours, the alive and dead of the spider mites were observed by means of a magnifying glam and, from the mortality, LC50 values were calculated according to Finney's simplified iconography to obtain the results as set forth in Table 8.

Test Example 9 Insecticidal effects on smaller brown planthoppers:

A rice seedling (height is 20 cm), which had elapsed l5 days after gennination, was immersed for l minute in an aqueous dilute emulsion at a given concentration of each of the present compounds in the form of emulsifiable concentrates. After air-drying, the rice seedling was put in a large test tube. into the test tube were liberated 20-30 smaller brown planthoppers, and the tube was covered with gauze. After 24 hours, the alive and dead of the planthoppers were observed and, from the mortality, LCSO values were calculated accord ing to Finneys iconography to obtain the results as set forth in Table 9,

TABLE 9 Compound No. LCSO (times) 120,000 10) 20,000 1 l l2,000 14) 38,000 16) 1 80,000 32,000 l8) 64,000 l9) 35,000 90,000 (22) 64,000 (24) 500,000 100.000

Test Example l0 A potted mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of spider mites, and was dusted by use of a bell jar duster with 4 Kg/ 10 ares of each of the present compounds in the form of 3 percent dusts. After the dusting, the plant was further parasitized on different days with two-spotted red spider mite adults, and the mortalities of the insects after 48 hours were individually investigated to obtain the results as set forth in Table 10.

Test Example ii A mottled kidney bean plant was grown to the 2 leaves stage in a flower pot of 9 cm in diameter. The root portion of the plant was sprinkled with 6 Kg/l ares of each of the present compounds in the form of 3 percent granules. After 3 days, the leaves of the plant were parasitized with a large number of two-spotted red spider mite adults. 72 Hours thereafter, the leaves were cut and taken up, and the alive and dead of the mites were observed with a magnifying glass to obtain the results as set forth in Table l I.

Test Example l2 A rice plant (variety: Waseasahi) at the offshoot stage, which had elapsed 30 days after planting, was transplanted in a pot, and eggs of rice stem borers immediately before hatching were laid on the stem of the plant. After 4 days, the plant was sprinkled with the present compound in the form of a granule. Five days thereafter, the plant was taken up from the pot and the stem was broken to observe the alive and dead of the larvae in the stem. The results were as set forth in Table TABLE I2 Compound Dose No of Mortality No. (Kg/l0 ares) tested (5) insects l0) 6 53 95.3 0.0-diethyl 0- Z-isopropyl- 6- methylt-pyrimidinyl) phosphorothioate 6 92 92.4

Test Example 1 3 A young mandarin orange tree of 3 years old was parasitized with a large number of arrowhead scales (Unapsis yanonensis). To the trunk of the tree (at a portion of 10 cm above the ground) was applied in the form of a ring 5 cc/lO cm of an emulsion formed by diluting to l ,000 times each of the present compounds in the form of 50 percent emulsifiable concentrates. On the day before, and 3, 7, l0 and 20 days afier of ap plication of the chemical, the habitat densities of the insects were investigated to obtain the results as set forth in Table 13.

Test Example 14 Preventive effects on rice blast:

A rice plant (variety: Waseasahi), which had been cultivated to the 3 leaves stage in a flower pot of 9 cm in diameter, was sprayed with 7 ml/pot of a given concentration emulsion of each of test chemicals in the form of emulsifiable concentrates. After 1 day, the plant was sprayed and inoculated with a spore suspension of rice blast fungus. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of the test chemicals, whereby the results as set forth in Table 14 were obtained.

TABLE 14 Active ingredient Control; trade name for a fungicide of Kumiai Chemical Co.

Preventive value was calculated according to the following equation:

Number of spots in Number of spots nonireatcd area. in treated area Preventive W H WW, A Number of spots in nontreated area value Test Example 15 A mottled kidney bean plant at the 2 leaves stage, which had elapsed 20 days after sowing, was parasitized with a large number of adults of two-spotted red spider mites (Terranychus telarius). The leaves of the kidney bean plants parasitized with said mites were immersed for 1 minute in an aqueous dilute solution of each of the present compounds in the form of wettable powders, and water was fed so as not to wither the leaves. After 48 hours, the alive and dead of the spider mites were observed by means of a magnifying glass and, from the mortality, LCSO values were calculated according to Finney's simplified iconography to obtain the results as set forth in Table 15.

Control Test Example 16 Insecticidal effects on smaller brown planthoppers:

A rice seedling (height 15-20 cm), which had elapsed l days after germination, was immersed for 1 minute in an aqueous dilute emulsion at a given concentration of each of the present compounds in the form of emulsifiable concentrates. After air-drying. the rice seedling was put in a large test tube. Into the test tube were liberated 20-30 smaller brown planthoppers, and the tube was covered with a wire net. After 24 hours, the alive and dead of the planthoppers were observed and, from the mortality, LC50 values were calculated according to Finneys iconography to obtain the results as set forth in Table [6.

TABLE 16 Compound No. LC50 (times) (28) l60,000 (29) 300,000 (30) 40,000 (32) 230,000 0,0-dimethyl O-( 3- methyl-4-nitrophenyl)- phosphorothioate 300,000

Control TABLE 17 After Aher After After Compound No. 3 days 5 days 9 days 13 days (28) I00 95.1 98.7 63.2 (29) I00 I00 994 92.1 (30) 92,3 51.4 30.2 0 (3l) 83.4 6L2 I344 7.8

0,0dimethyl s-( N- meth ylcarbarnoyl )meth yl phosphorodithioate 91.4 10. 3 6.2

Control Test Example 18 A mottled kidney bean plant was grown to the 2 leaves stage in a flower pot of 9 cm in diameter. The root portion of the plant was sprinkled with 6 Kg/IO arcs of each of the present compounds in the form of 3 percent granules. After 3 days, the leaves of the plant were parasitized with a large number of two-spotted red spider mite adults. Afier 72 hours, the leaves were cut and taken up, and the alive and dead of the mites Test Example 19 A rice plant at the offshoot stage, which had elapsed 30 days after planting, was transplanted in a l/l00,000 Wagner pot, and eggs of rice stern borers immediately before hatching were laid on the stem of the plant. After 10 days, the plant was taken up from the pot, and the stem was broken to observe the alive and dead of the larvae in the stem. The results were as set forth in Table 19.

TABLE I9 Compound Dose No. of Mortality No. (Kg! 1 0 ares) tested insects (28) 6 25 I (29) 6 53 100 (32) 6 82 100 0,0-diethyl o-(2- isopropyl-6- methyl-4-pyrimidinyl )phosphorothioate 6 94 92.4

Control Test Example 20 A young mandarin orange tree of 3 years old was parasitized with a large number of arrowhead scales (Unapsis yanonensis). To the trunk of said tree (at a portion of IO cm above the ground) was applied in the form of a ring 2 cc/lO cm of an emulsion formed by diluting to 1,000 times each of the present compounds in the form of emulsifiable concentrates. On the day before, and 3, 7, l0 and 20 days after of application of the chemical, the habitat densities of the insects were investigated to obtain the results as set forth in Table 20.

TABLE 20 Day before Days after lpplicaapplication tion of chemical Test Example 21 Fungicidal activities (Preventive effects on rice blast):

A rice plant (variety: Waseasahi), which had been cultivated to the 3 leaves stage in a flower pot of 9 cm in diameter, was sprayed with 7 ml/pot of a given concentration emulsion of each of the present compounds in the form of emulsifiable concentrates. After I day, the plant was sprayed and inoculated with a spore suspension of rice blast fungus. 4 Days thereafter, the number of spots generated was counted to investigate the fungicidal effects of individual compounds. whereby the results as set forth in Table 21 were obtained.

Active ingredient Emulsifier (In Compound (1) 50 Compound (3) 20 Xylene 3O Cyclo hexanone 50 Sorpol 2020 20 Sorpol 2492 30 Sorpol: Registered trade name for an emulsifier produced by Toho Chemical Co.

Example 2 Formulation of wettable powders:

40 Parts of the compound (5) and 5 parts of Sorpol 5029 (registered trade name for an emulsifier produced by Toho Chemical Co.) were thoroughly mixed together. This mixture was kneaded, while being dropped, with 55 parts of 200 mesh talc, which was under thorough stirring in a mortar, whereby a wettable powder was obtained. In application, the powder was diluted with water and the resulting solution was sprayed.

Example 3 Formulation of dusts:

In such proportion as shown in the table below, each of the compounds set forth in the table was dissolved in a small amount of acetone, and the solution was thoroughly mixed with 200 mesh talc. Thereafier, the acetone was removed by vaporization to obtain a dust of each compound. ln applica tion, the dust was dusted as it was.

Active ingredient ('12) Extender (k Compound (3) 2 Talc 98 Compound (6) 4 Talc 96 Example 4 Formulation of granules:

In such proportion as shown in the table below, each of the present compounds was mixed with the binder and extender in the order set forth in the table. This mixture was kneaded with a small amount of water, was granulated by means of a granulator and was then dried to obtain a granule. 1n application, the granule was sprinkled as it was.

Example 5 Preparation of compound l Into a solution of 5.6 g. of potassium hydroxide in 50 ml. of ethyl alcohol was dropped at room temperature 16.9 g. of 0,0-diethyl-phosphorothionoamidate, and the mixture was refluxed with stirring for 8 hours. Subsequently, 19.9 g. of 1,3- diethylthio-2-chloropropane was further dropped into the mixture at 4050 C. over a period of 30 minutes, and the resulting mixture was refluxed with stin'ing for 2 hours. After removing the solvent by distillation, the residue was charged with toluene, was washed with 5 percent sodium carbonate and then with water, and was dried over anhydrous sodium sulfate. Thereafter, the toluene was removed by distillation under reduced pressure to obtain 25.8 g. of yellow oily O- ethyl-S-( 2-ethylthiol -ethylthiomethyl )-ethylphosphorothioamidate, n l.5497.

Elementary analysis for C;H,,NO,PS3:

Calculated (96) Found ('k) P 10.21 9.62 S 31.70 3l.54 N 4.61 4.33

Example 6 Preparation of compound (2): 5.6 g. of potassium hydroxide was reacted with l6.9 g. of 0,0-diethyl-thionoamidate in entirely the same manner as in Example 5. Into the reaction liquid was dropped at room temperature over a period of IS minutes 18.3 g. of l-ethylthio-3 ethoxy-2-chloropro ane, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 5 were effected to obtain 23.3 g. of a pale yellow oily O- ethyl-S-(2-ethylthio-1-ethoxymethyl)ethylphosphorothioamidate. u I5 I48.

Elementary analysis for C,H,,NO,PS,:

Calculated (12) Found (in P 10.78 l0.61 S 22.32 22.01 N 4.31 4.4.3

Example 7 Preparation of compound (3):

Into a solution of 8.0 g. of sodium hydroxide in 100 ml. of ethyl alcohol was dropped at room temperature over a period of 30 minutes 28.2 g. of 0,0-dimethylhosphorothionoamidate, and the mixture was refluxed with stirring for 5 hours. After removing the methyl alcohol by distillation under reduced pressure, a crystal deposited was suspended in ethyl ether, and the suspension was filtered to obtain 28.3 g. of a white crystal of sodium O-methylphosphorothioamidate.

14.9 g. of this crystal was dissolved in 50 ml. of methyl alcohol and was charged with 16.9 g. of l-ethylthio-3-methoxy- 2-chloropropane, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 5 were effected to obtain 23.0 g. of pale yellow oily O-methyl-S- 2-ethylthio- 1 -methoxymethy1)-ethyl-phosphorothioamidate, n 1.5125.

Elementary analysis for C,H ,NO PS,:

Calculated (91:) Found P l 1.94 1 L70 5 24.73 25.23 N 5.40 5.l2

Example 8 Preparation of compound (4):

4.0 g. of sodium hydroxide was reacted with 14.1 g. of 0,0- diemthyl-phosphorothionoamidate in entirely the same manner as in Example 5. To the reaction liquid was added 21.1 g. of l-iso-propylthio-3-n-propoxy-2-chloropropane, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 5 were effected to obtain Preparation of compound (5 )1 To a solution of 15.2 g. of sodium O-methylphosphorothioamidate in 50 ml. of water was added 18.3 g. of l-ethylthio-3-ethoxy-Z-chloropropane, and the mixture was stirred at 60 70 C. for 4 hours.

After cooling, the mixture was treated in the same manner as in Example 5 to obtain 24.6 g. of reddish brown oily O- methy1-S-( 2-ethylthiol -ethoxymethyl )-ethylphosphorothioamidate, n 1 .5169.

Elementary analysis for C,H, ,NO,PS,:

Calculated (91") Found (36) P l 1.33 l 1.13

Example Preparation of Compound (6):

To a solution of 18.2 g. of potassium O-ethylphosphorothioamidate in 50 ml. of ethyl alcohol was added 16.8 g. of l-ethylthio-3-emthoxy-2-chloropropane, and the mixture was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 5 were effected to obtain 25.2 g. of pale yellow oily O-ethyl-S-( 2-ethylthio-l-methoxymethyl)-ethyl-phosphorothioamidate, n 1.5158.

Elementary analysis for C,H,,,NO,PS,:

Calculated (9k) Found (12) P 1 1.33 11.25 S 2346 22.97 N 5.12 5.08

Example 1 1 Preparation of compound (7):

To a solution of 15.2 g. of sodium O-methylphosphorothioamidate in 50 ml. of methyl alcohol was added 19.6 g. of 1-n-butylthio-3-methoxy-2-chloropropane, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 5 were effected to obtain 25.8

Formulation of ernulsifiable concentrates:

Each of the compounds shown in the table below was thoroughly mixed successively with given proportions of the solvent and emulsifier set forth in the table to obtain a homogeneous emulsifiable concentrate. In application, the concentrate was diluted with water, and the resulting emulsion was sprayed.

Emulsifierti) Active ingredient Solvent Compound (8) 50 Compound (14) 20 Xylene 3O Cyclohexanone 50 Sorpol 2020 20 Sorpol 2492 30 Registered trade name for an emulsifier produced by Toho Chemical Co.

Example 13 Formulation of wettable powder:

40 Parts of the compound (3) and 5 parts of Sorpol 5029 (registered trade name for an emulsifier produced by Toho Chemical Co.) were thoroughly mixed together. This mixture was kneaded, while being mixed, with 55 parts of 200 mesh talc, which was under thorough stirring in a mortar, whereby a wettable powder was obtained. In application, the powder was diluted with water and the resulting solution was sprayed. Example 14 Formulation of granules:

ln such proportions as shown in the table below, each of the present compounds was mixed with the binder and extender in the order described in the table. This mixture was kneaded with a small amount of water, was granulated by means of a granulator and was then dried to obtain a granule. 1n application, the granule was sprinkled as it was.

Active ingredient Binder (56) Extender ("kl Compound (1 l 2 Sodium lignin Clay 97 sull'onate Compound (13) 5 Sodium lignin Clay 93 sulfonate Active ingredient Extender (k Compound (9) 2 Talc 98 Compound l2) 4 Talc 96 Example 16 Preparation of compound (8):

A solution of 11.2 g. of potassium hydroxide in 100 m1. of ethyl alcohol was saturated, under cooling, with hydrogen sulfide to prepare an ethyl alcohol solution of potassium hydrosulfide. To this solution was added at room temperature 39.4 g. of 0,0diethyl-N-ethyl-phosphorothionoamidate, and the mixture Wm refluxed with stirring for 17 hours. After removing the solvent by distillation under reduced pressure, the mixture was charged with acetone to remove insolubles, and then the acetone was removed by distillation under reduced pressure. The residue was dissolved in water and the solution was washed with toluene. From the aqueous layer, water was removed by distillation under reduced pressure to obtain 20.0 of a milk-white crystal of wettable potassium O ethyl-N-ethyl-phosphorothioamidate.

11.0 g. of this crystal was dissolved in 50 ml. of ethyl alcohol. To this solution was added at room temperature 8.4 g. of 1ethylthio-3 3-methoxy-2-chloropropane, and the mixture was refluxed with stirring for 2.5 hours. After removing the solvent by distillation under reduced pressure, the residue was charged with toluene, and was washed with 3 percent sodium hydrogencarbonate and then with water. Thereafier, the toluene was removed by distillation under reduced pressure to obtain 13.5 g. of reddish orange oily O-ethyl-S-(Z-ethylthiolmethoxymethyl)-et.hyl-N-ethyl-phosphorothioamidate, u 1.5080.

Elementary analysis for C,,,H,,NO:,PS,:

Calculated Found P [0.28 10.18 S 21.28 21.22 N 4.65 4.55

Example 17 Preparation of compound (9):

An ethyl alcohol solution of potassium hydrosulfide was prepared in the same manner as in Example 16 from 100 ml. of ethyl alcohol, 1 1.2 g. of potassium hydroxide, and hydrogen sulfide. To the said solution was added 45.0 g. of 0,0-diethyl- N,N-diethyl-phosphorothionoamidate, and the mixture was refluxed with stirring for 17 hours. The mixture was treated in the same manner as in Example 16 to obtain l5.l g. ofa milkwhite crystal of potassium O-ethyl-N,N'diethylphosphorothioamidate.

12.0 g. of this crystal was mixed with 8.4 g. of l-ethylthio-3- methoxy'lchloropropane and 50 ml. of ethyl alcohol, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatment as in Example 16 were effected to obtain 14.9 g. of reddish brown oily O-ethyl-S-( Z-ethylthio-l-methoxymethyll-ethyl-N,N-diethyl-phosphorothioamidate, n L498 1.

Elementary analysis for C ,H,,NO,PS,:

Calculated (96) Found P 9.40 9.59 8 19.49 19.36 N 4.25 4.01

Example 18 Preparation of compound An ethyl alcohol solution of potassium hydrosulfide was prepared in the same manner as in Example 16 from I00 ml. of ethyl alcohol, 1 1.2 g. of potassium hydroxide, and hydrogen sulfide. To this solution was added 42.0 g. of 0,0-diethyl-N-npropyl-phosphorothionoamidate, and the mixture was refluxed with stirring for hours. Subsequently, the mixture was treated in the same manner as in Example 16 to obtain 19.1 g. of a white crystal of potassium O-ethyl-N-n-propylphosphorothioamidate.

l 1.5 g. of this crystal was mixed with 8.4 g. of l-ethylthio-3- methoxy-2-chloropropane and 50 ml. of water, and the mixture was stirred at 60- 70 C. for 3 hours. Thereafter, the oil layer was separated, was washed with 3 percent sodium hydrogencarbonate and then with water, and was dried over anhydrous sodium carbonate to obtain 14.4 g. of pale yellowish green oily O-ethyl-S-(Z-ethylthio-l-methoxymethyl)- ethyl-N-n-propyl-phosphorothioamidate, u 1.5038.

Elementary analysis C, H-NO,PS,:

Calculated (11) Found (55) P 9.82 9.47 S 20.3 3 20.3 3 N 4.44 4.45

Example 1 9 Preparation of compound 1 1 An ethyl alcohol solution of potassium hydrosulfide was prepared in the same manner as in Example 16 from ml. of ethyl alcohol, 1 1.2 g. of potassium hydrosulfide, and hydrogen sulfide. To this solution was added 45.0 g. of 0.0- diethyl-N-n-butyl-phosphorothionoamidate, and the mixture was refluxed with stirring for 18 hours. Subsequently, the mixture was treated in the same manner as in Example 16 to obtain 23.8 g. ofa white crystal of potassium O-ethyl-N-n-butylphosphorothioamidate.

12.0 of this crystal was mixed with 9.8 g. of l-n-butylthio-3- methoxy-Z-chloropropane and 50 ml. of ethyl alcohol, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 16.3 g. of yellow oily O-ethyl-S-( 2-n-butylthiol-methoxymethyl )-ethyl-N-n-butyl-phosphorothioamidate, n 1 .4985.

Elementary analysis for C .H,,NO,PS,:

Calculated (I) Found (9%) P 8.66 8.71 S [7.94 17.78 N 3.92 405 Example 20 Preparation of compound 12):

14.0 g. of a white crystal of potassium O-ethyl-N-benzylphosphorothioamidate obtained in the same manner as in Example 16 was mixed with 8.4 g. of l-ethylthio-3-methoxy-2- chloropropane and 50 ml. of ethyl alcohol, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatment as in Example 16 were effected to obtain 16.6 g. of reddish brown oily O-ethyl-S-( Z-ethylthio-l-methoxymethyly ethyl-N-benzyl-phosphorothioamidate, 12,," l .5449.

Elementary analysis for C.,H,,N0,PS,:

Calculated Found f'k] P 8.52 8.41 S l7.64 17.89 N 3.85 3.65

Example 21 Preparation of compound 13):

13.5 g. of a white crystal of O-ethyl-N-cyclohexylphosphorothioamidate obtained in the same manner as in Example 16 was mixed with 8.4 g. of l-ethylthio-3-methoxy-2- chloropropane and 50 ml. of ethyl alcohol, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 15.4 g. of yellow oily O-ethyl-S-( 2-ethylthio- 1 -methoxymethyl )-ethyl-N- cyclohexyl-phosphorothioarnidate, n,," l .5 179.

Elementary analysis:

Calculated '5) Found (k) P 8. 71 8.7 3 8 18.04 17.68 N 3.94 3.97

Example 22 Preparation of compound 14):

13.0 g. of a yellowish green viscous liquid of potassium 0- ethyl-N-phenyl-phosphorothioamidate obtained in the same manner as in Example 16 was mixed with 8.4 g. of l-ethylthio 3-methoxy-2-chloropropane and 50 m1. of ethyl alcohol, and the mixture was refluxed with stirring for 3 hours. Thereafter, the same treatments as in example 16 were effected to obtain 15.8 g. of O-ethy1-S-(Z-ethylthio-l-methoxymethyl)-ethyl-N- phenyl-phosphorothioamidate, n 1.5558.

Elementary analysis for C H NO,PS,:

Calculated Found (16) P 8.86 9.09 S 18.35 17.92 N 4.01 4.23

Example 23 Preparation of compound 17):

A methyl cellosolve solution of potassium hydrosulfide was prepared in the same manner as in Example 16 from 100 ml. of methyl cellosolve, l 1.2 g. of potassium hydroxide, and hydrogen sulfide. To this solution was added 31.0 g. of 0,0- dimethyl-N-methyl-phosphorothionoamidate, and the mixture was stirred at 95 100 C. for 4 hours. After removing the solvent by distillation under reduced pressure, the mixture was dissolved in water and the solution was washed with toluene. From the aqueous layer, water was removed by distillation under reduced pressure to obtain quantitatively a white crystal of wettable potassium O-methyl-N-methylphosphorothioamidate.

9.9 gv of this crystal was mixed with 8.4 g. of l-ethylthio-3- methoxy-Z-chloropropane and 50 ml. of methyl alcohol, and the mixture was refluxed with stirring for 2 hours. Thereafter, the same treatment as in Example 16 were effected to obtain 12.3 g. of yellow oily O-methyl-S-( 2-ethylthio-l-methoxymethyl)-ethyl-N-methyl-phosphorothioamidate, 11, I .5 160.

Elementary analysis for C,;l-l, NO,PS,:

Calculated (1%) Found (5) P l l .33 1 1.46

Example 24 Preparation of compound I 8):

A mixture comprising a white crystal of wettable potassium O-methyl-N-n-propyl-phosphorothioamidate obtained in the same manner as in Example 23, 8.4 g. of l-ethy1thio-3- methoxy-Z-chloropropane and 50 ml. of methyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.4 g. of yellow oily O-methyl-S-( 2-ethylthio-l-methoxymethyl)-ethyl-N- n-propyl-phosphorothioamidate, 21 1.5920.

Elementary analysis for C,.,H,.N0,PS.;

Calculated (kl Found (95) P 10.28 10.12 5 21.28 20.79 N 4.65 4.51

Example 25 Preparation of compound (27 A mixture comprising 11.4 g. of potassium O-methyl-N-npropyl-phosphorothioamidate, 7.7 g. of l-methylthio-3- methoxy-Lchloropropane and 50 ml. of methyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.3 g. of yellow oily O-methyl-S-(Z-rnethylthio-l-methoxymethyl)-ethyl- N-n-propyl-phosphorthionoamidate, n,,- 1.5067.

Elementary analysis for C,H,,NO,PS,:

Calculated (I) Found P 10.78 10.72 S 22.31 21.94 N 4.87 4.80

Example 26 Preparation ofcompound 19):

A mixture comprising 1 1.4 g. of a white crystal of wettable potassium O-methyl-N-iso-propyl-phosphorothioamidate obtained in the same manner as in Example 23, 8.4 g. of 1- ethylthio-3-methoxy-Z-chloropropane and 50 ml. of methyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.7 g. of yellow oily O-methyl-S-(Z-ethylthio-l-methoxymethyl)-ethyl-N-iso-propyl-phosphorothionoamidate, 11 1 .5072.

Elementary analysis for C ,H NO,PS,:

Calculated (5) Found (5) P 10.28 9.97 S 2128 21106 N 4.65 4.38

Example 27 Preparation of compound 20):

A mixture comprising 12.1 g. of a white crystal of wettable potassium O-rnethyl-N-n-butyl-phosphorothioamidate obtained in the same manner as in Example 23, 8.4 g. of lethylthio-3-methoxy-2-chloropropane and 50 ml. of methyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 14.4 g. of yellow oily O-methyl-S-(Z-ethylthio-l-methoxymethyl )-ethyl-N-n-butyl-phosphorothionoamidate, n 5

Elementary analysis for C 1-1,,NO,PS,:

Calculated (k1 Found P 9.82 9.80 5 20.33 19.84 N 4.44 4.40

Example 28 Preparation of compound (21 )2 A methyl cellosolve solution of potassium hydrosulfide was prepared in the same manner as in Example 16 from 100 ml. of methyl cellosolve, 1 1.2 g. of potassium hydroxide, and hydrogen sulfide. To this solution was added 36.7 g. of 0,0- diethyl-N-methyl-phosphorothionoamidate, and the mixture was stirred at C. for 6 hours. Subsequently, the mixture was treated in the same manner as in Example 16 to obtain 30.9 g. of a white crystal of wettable potassium O-ethyl-N- methyl-phosphorothioamidate.

10.6 g. of this crystal was mixed with 8.4 g. of l-ethylthio-3- methoxy-Z-chloropropane and 50 ml. of ethyl alcohol, and the mixture was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.3 g. of yellow oily O-ethyl-S-( 2-ethylthiol -methoxymethyl )-ethyl-N-methyl-phosphorothioamidate, n 5

Elementary analysis for C,H,,NO,PS,:

Calculated Found P 10.78 10.58 S 22.31 22.47 N 4.87 4.64

Example 29 Preparation of compound (24 )2 A mixture comprising 10.6 g. of potassium O-ethyl-N- methyl-phosphorothioamidate, 7.7 g. of l-methylthio-3- methoxy-Z-chloropropane and 50 ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 12.9 g. of pale yellow oily O-ethyl-S-( 2methy1thio-l-methoxymethyU-ethyl- N-methyl-phosphorothioamidate, n 1.5097.

Elementary analysis for C,H, NO,PS,:

Calculated (11) Found P 1 1 .3 3 10.98 S 23.45 23.00 N 5.12 5 .08

Example 30 Preparation of compound (25):

A mixture comprising 10.6 g. of potassium O-ethyl-N- methyl-phosphorothioamidate, 9.1 g. of l-isopropylthio-3- methoxy-Z-chloropropane and 50 ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.2 g. of pale yellowish green oily O-ethyl-S-(2-isopropylthio-1-methox- A mixture comprising 10.6 g. of potassium O-ethyl-N- methyl-phosphorothioamidate, 9.8 g. of 1-ethylthio-3- isopropyloxy-2-chloropropane and 50 ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 13.9 g. ofO- ethyl-S-( 2-ethylthiol-isopropyloxy)-ethyl-N-methylphosphorothioamidate, r1 1.4981.

Elementary analysis for C,|H"NO,PS,:

Calculated (96) Found (96) Example 32 Preparation of compound (22):

A mixture comprising 12.1 g. of a white crystal of wettable potassium O-ethyl-N-isopropyl-phosphorothioamidate obtained in the same manner as in Example 28, 8.4 g. of 1- ethy1thio-3-methoxy-2-chloropropane and 50 ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16, were effected to obtain 14.5 g. of pale yellow oily O-ethyl-S-(2-ethylthio-l-methoxymethyl )-ethyl-N-isopropyl-phosphorothioamidate, "D2" 5 1.5020.

Elementary analysis for C H,,NO,PS,:

Calculated Found (k) Example 33 Preparation of compound (23):

A mixture comprising 12.9 g. of a white crystal of wettable potassium Oethyl-N-sec-butyl-phosphorothioamidate, 8.4 g. of l-ethylthio-3-methoxy-2-chloropropane and ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 16 were effected to obtain 15.2 g. of yellow oily O-ethyl-S-(Z-ethylthio-l-methoxymethyl)-ethyl-N-sec-butyl-phosphorothioamidate, 11 5 1.4992.

Elementary analysis for C,,H,,,N0,PS,:

Calculated Found (96) P 9.40 9.32 S 19.46 19.35 N 4.25 4.09

Example 34 Formulation of emulsifiable concentrates:

Each of the compounds set forth in the table below was thoroughly mixed successively with the solvent and emulsifier in such proportions as shown in the table to obtain a dust. In application, each dust was dusted as it was.

Active ingredient (36) Solvent Emulsifier (I) Compound(28) 50 Compound(30) 20 Xylene 30 "Sorpol 2020 20 Cyclohexanone S0 Sorpol 2492 30 Registered trade name for an emulsifier produced by Toho Chemical Co.

Example 35 Fonnulation of wettable powder:

40 Parts of the compound (30) was thoroughly mixed with 5 parts of Sorpol 5029 (registered trade name for an emulsifier produced by Toho Chemical Co. This mixture was kneaded, while being dropped, with 55 parts of 200 mesh talc, which was under thorough stirring in a mortar, to obtain a wettable powder. In application, the powder was diluted with water, and the solution was sprayed.

Example 36 Formulation of granules:

In such proportions as set forth in the table below, each of the compounds shown in the table was mixed with the binder and emulsifier in this order. Subsequently. the mixture vim kneaded with a small amount of water, was granulated by means of a granulator and was then dried to obtain a granule. In application, the granule was sprinkled as it was.

Active ingredient Binder Extender (1) Compound (28) 2 Sodium lignin Clay 97 sulfonate 1 Compound (29) 5 Sodium lignin Clay 93 sulfonate Active ingredient Extender (9c) Compound (30) 2 Talc 98 Example 38 Preparation of compound (28):

A solution of l 1.2 g. of potassium hydroxide in 100 ml. of methyl cellosolve was saturated, under cooling, with hydrogen sulfide to prepare a methyl cellosolve solution of potassium hydrosulfide. To this solution was added at room temperature 36.2 g. of 0,0-dimethyl-N-allyl-phosphorothionoamidate, and the mixture was stirred at 14 C. for 5 hours. After removing the solvent by distillation under reduced pressure, the mixture was charged with acetone to remove insolubles, and then the acetone was removed by distillation under reduced pressure. Subsequently, the residue was dissolved in water, and the solution was washed with toluene. From the aqueous layer, water was removed by distillation under reduced pressure to obtain 40.9 g. of a white crystal of wettable potassium O-methyl-N-allyl-phosphorothioamidate.

11.3 g. of this crystal was dissolved in 50 ml. of methyl a1- cohol and was charged with 8.4 g. of 1-ethy1thio-3-methoxy-2- chloropropane, and the mixture was refluxed with stirring for 2 hours. After removing the solvent by distillation under reduced pressure, the residue was charged with water and chloroform, and the chloroform layer was dried over anhydrous sodium sulfate. Thereafter, the chloroform was removed by distillation under reduced pressure to obtain 13.7 g. of yellow oily O methyl-S-( Z-ethylthio-l-methoxyethyl)- ethyl-N-allyl-phosphorothioamidate, 11 1.5180.

Elementary analysis for C H NOJQ:

Calculated (91;) Found P 10.35 10.36 S 21.42 21.71 N 4.68 4.86

Example 39 Preparation of compound (29):

A mixture comprising 11.3 g. of potassium O-methyl-N- allyl-phosphorothionoamidate, 7.7 g. of 1-methy1thio-3- methoxy-Z-chloropropane and 50 ml. of methyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 38 were effected to obtain 12.4 g. of yellow oily -methyl-S-(2-methy1thio-l-methoxymethyl)-ethyl- N-allyl-phosphorothioamidate, n 1.5193.

Elementary analysis for C,H, NO,PS,:

Calculated Found (k) P 10.85 10.74 22.47 21.96 N 4.91 4.70

Example 40 Preparation of compound (30):

A mixture comprising 12.0 g. of a white crystal of wettable potassium 0-ethyl-N-allyl-phosphorothionoarnidate obtained in the same manner as in Example 38, 8.4 g. of l-ethylthio-3- methoxy-2-chloropropane and 50 ml. of ethyl alcohol was refluxed with stirring for 2 hours. Thereafter, the same treatments as in Example 38 were effected to obtain 14.9 g. of yellow oily O-ethyl-S-( 2-ethylthio-l-methoxy-ethyl)-ethyl-N- a1lyl-phosphorothioamidate, n,,' 5 1.5104.

Elementary analysis for C H,J-IO,FS,:

Calculated (76) Found (I) Example 4] Preparation of compound (31):

A methyl cellosolve solution of potassium hydrosulfide was prepared from 100 m1. of methyl cellosolve, 11.2 g. of potassium hydroxide. and hydrogen sulfide. To this solution was added 44. 2 g. of 0,0-dimethyl-N,N-diallylphosphorothionoamidate, and the mixture was stirred at 95-l00bL C. for 4 hours. Subsequently, the mixture was Elementary analysis for C H NO;PS,:

Calculated (96) Found (35) P 9. l 2 8.93 S 18.89 [8.71 N 4.13 4.l3

What we claim is: l. A phosphorothioamidate having the formula,

wherein R is alkyl having up to 4 carbon atoms, R, and R, are individually hydrogen, alkyl having up to 10 carbon atoms, cyclohexyl, phenyl, aralkyl having up to eight carbon atoms or an alkenyl having up to five carbon atoms, R and R, are each alkyl having up to five carbon atoms, and X is oxygen or sulfur.

2. A phosphorothioamidate according to claim 1, wherein R, and R are hydrogen.

3. A phosphorothioamidate according to claim I, wherein R, and R are individually hydrogen alkyl having up to 10 carbon atoms, cyclohexyl phenyl or aralkyl having up to eight carbon atoms and are not hydrogen simultaneously.

4. A phosphorothioamidate according to claim I, wherein R and R are individually hydrogen or alkenyl having up to five carbon atoms and are not hydrogen simultaneously.

5. A compound of the formula 0 CII Oi SCHCH2-S'C2Hr NH HZOCHJ 6. A compound of the formula 0 CII3Oi S-CH-CHz- S'CQHS ILH! CI-IzOCH 7. A compound of the formula 0 CzH OI -SCHCH2-S-C2H5 NH; IHzOCIh 8. A compound of the formula 0 CgIIbOi SCH CHrSCHa CHgOCH;

NH2CH3 9. A compound of the formula 9 CH O-i -s-CHCm-SCQHE UNITE!) S'IATES PATENT O'FE' ICE (IEGH'IIFICA'IIG ()1 (IORRE ITION June 13, 1972 3 6:79 057 H w Dated lut uni: No. WW

Inventor(s) Hiroshi Tsuchiya et a1.

1t is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Please insert the following missing claim for priority:

-Japanese No. 82964/68 filed November 12, 1968; Japanese No. 95735/68 filed December 25, 1968; Japanese No. 82124/69 filed October 13, 1969-- Signed and sealed this 6th day of February 1973.

(SEAL) Attest:

EDWARQMJLETCIEE ,JR. ROBERT GOTTSCHALK ALtGStlng Officer Commissioner of Patents USCOMM-DC UO370-POD n u cnvrnmurm PIIHHING mrlrl I069 0- 165-311 I' UMM (O-1050 ilO-(KH 

2. A phosphorothioamidate according to claim 1, wherein R2 and R3 are hydrogen.
 3. A phosphorothioamidate according to claim 1, wherein R2 and R3 are individually hydrogen alkyl having up to 10 carbon atoms, cyclohexyl phenyl or aralkyl having up to eight carbon atoms, and are not hydrogen simultaneously.
 4. A phosphorothioamidate according to claim 1, wherein R2 and R3 are individually hydrogen or alkenyl having up to five carbon atoms and are not hydrogen simultaneously. 